JP2007197690A - Method for producing hydroxyl-terminated acrylic acid compound polymer at both ends and the polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polymer economically by a simple process without using a special reaction reagent, and does not contain an atom that deteriorates physical properties, and has hydroxyl groups at both terminals. Provided is a method for producing a hydroxyl-terminated acrylic acid compound polymer which can be produced while controlling a polymer which is only a primary hydroxyl group or a primary and secondary hydroxyl group, and further the hydroxyl groups at both ends are only primary or primary. It is another object of the present invention to provide a novel both-end hydroxyl group acrylic acid compound polymer that is secondary and secondary.
The object of the present invention is to (1) a method for producing an acrylic acid compound polymer having hydroxyl groups at both ends, characterized by subjecting an acrylic acid compound to radical polymerization reaction using an OH radical as an initiator, and (2) Solved by the above production method using hydrogen peroxide and ferrous salt as OH radical generator, (3) any one of the above production methods using a mixed solvent of acetonitrile and water or a mixed solvent of ethanol and water as a reaction solvent. The
[Selection] Figure 6

Description

  The present invention relates to a process for producing an acrylic acid compound polymer having hydroxyl groups at both molecular terminals (both terminal hydroxyl group acrylic acid polymer). More specifically, the hydroxyl groups at both molecular terminals are either primary hydroxyl groups or primary and secondary. The present invention relates to a process for producing a hydroxyl-terminated acrylic acid compound polymer at both ends, which can be adjusted to be a hydroxyl group and can be produced economically by a simple process, and the polymer. In the present invention, a primary hydroxyl group represents a hydroxyl group bonded to a primary carbon atom, and a secondary hydroxyl group represents a hydroxyl group bonded to a secondary carbon atom.

  An acrylic acid compound polymer having hydroxyl groups at both ends of the molecule (both end hydroxyl group acrylic acid polymer) can directly utilize the reactivity of the hydroxyl groups at both ends, and can convert hydroxyl groups to other functional groups. Since the reactivity can also be utilized, a polymer compound having good physical properties in terms of toughness, heat resistance, durability, and the like can be obtained by making it linear and / or network easily. For example, in various resins such as a polyester resin, a polyurethane resin, and a polycarbonate resin, it is desirable to use a hydroxyl-terminated acrylic acid ester polymer as both-terminal hydroxyl-acrylate compound polymer as a resin raw material without damaging the original physical properties of the resin. A resin with improved physical properties can be obtained.

  In recent years, a number of methods for producing such a both-end hydroxyl group acrylate compound polymer (particularly both-end hydroxyl group acrylate polymer) have been proposed together with the polymer. For example, Patent Document 1 discloses that a halogen-terminated telechelic polymer is obtained by polymerizing an acrylate ester in the presence of a halogen-containing hydrocarbon compound (chain transfer agent) and a polymerization initiator, and this is hydrolyzed or a diol. A method for producing a hydroxyl-terminated acrylate polymer by reacting with a compound or the like is disclosed.

  However, in this method, a halogen-terminated telechelic polymer is once produced using a halogen-containing hydrocarbon compound, and then the desired polymer is produced. Therefore, the production process becomes complicated, and the polymer is economically produced by a simple process. In addition, there are problems such as adverse effects on the environment due to the use of a large amount of halogen-containing hydrocarbon compounds. Moreover, the polymer obtained has terminal hydroxyl groups of primary and secondary hydroxyl groups, and both terminals are not primary hydroxyl groups.

  Patent Document 2 discloses a method for producing a both-end hydroxyl group acrylate ester polymer by polymerizing an acrylate ester using a sulfur-containing diol compound (chain transfer agent) and a polymerization initiator. However, in this method, since a sulfur-containing diol compound is used for the chain transfer agent, there is a problem that the obtained polymer contains a sulfur atom and its physical properties (weather resistance, heat resistance, etc.) are gradually impaired. there were.

  Patent Document 3 discloses that a vinyl polymer having a hydroxyl group at one end is reacted with a compound having both a polymerizable alkenyl group and a hydroxyl group, or a vinyl polymer having a highly reactive carbon-halogen bond at one end. Depending on whether a hydroxyl group-containing oxyanion compound or a hydroxyl group-containing stabilized carbanion is reacted, or a halogenated group of a vinyl polymer having a hydroxyl group at one end and a halogen group at the other end is subjected to a coupling reaction, etc. A method for producing an acrylate polymer is disclosed.

  However, in this method, since a vinyl polymer as a precursor is produced and then this is reacted with the hydroxyl group-containing compound or a coupling reaction to introduce a hydroxyl group, the production process is complicated. Thus, it was difficult to produce a polymer simply. Moreover, when making it react with a hydroxyl-containing compound, the special compound which has a hydroxyl group is required, and when making a coupling reaction, a coupling agent (polythiol, polyamine, polyol, etc.) is newly needed, and the polymer obtained In some cases, sulfur atoms are contained and the physical properties are gradually impaired.

  Patent Document 4 discloses a novel double-terminal hydroxyl acrylic acid by polymerizing an acrylic ester using an iodine-containing aromatic compound (chain transfer agent) and then reacting the resulting polymer with a hydroxyl-containing amine compound. A method for producing an ester polymer is disclosed. However, this method also has a problem in that the production process is complicated, and the obtained polymer contains nitrogen atoms and the physical properties are gradually deteriorated.

  In Patent Document 5, an acrylic ester is polymerized in the presence of a special organometallic catalyst, a lactone is added at the end of polymerization to block copolymerize the lactone, and then the alcohol is added to stop the polymerization. A method for producing a terminal hydroxylated acrylic polymer is disclosed. However, in this method, there is a problem that the production process is complicated in addition to using a special catalyst, and the resulting polymer is also a hydroxyl group at one end (secondary hydroxyl group), but the other end is unknown. It was difficult to obtain a terminal having a hydroxyl group (particularly a primary hydroxyl group).

In Patent Document 6, methyl dichloroacrylate is reacted with butyl acrylate in the presence of cuprous chloride and 2,2′-bipyridine, and then allyl alcohol and a large excess of cuprous chloride or zero-valent copper are reacted. In addition, a method for producing an acrylate polymer in which both ends are primary hydroxyl groups by reaction is disclosed. However, in this method, a chain reaction is carried out using methyl dichloroacrylate as a starting material, and then allyl alcohol is reacted to obtain the desired product. Furthermore, reaction raw materials other than butyl acrylate (methyl dichloroacrylate, allyl alcohol) are obtained. ) And a large amount of copper compound or copper, the manufacturing process is not only complicated, but also requires a post-treatment of copper, making it difficult to economically produce a polymer in a simple process. there were.
JP-A-4-132706 JP-A-5-262808 JP 2000-53723 A JP 2001-163918 A JP 2001-81129 A US Patent Application Publication No. 2003/0151825

  As described above, none of the conventional methods for producing an acrylic acid compound polymer having hydroxyl groups at both ends of a molecule (both end hydroxyl group acrylic acid compound polymers) is satisfactory. In view of such circumstances, an object of the present invention is to provide a method capable of solving the above-described problems and producing a both-end hydroxyl group acrylic acid compound polymer.

  That is, according to the present invention, a polymer can be produced economically by a simple process without using a special reaction reagent, does not contain an atom that lowers the physical properties, and both terminal hydroxyl groups are one. It is an object of the present invention to provide a method for producing a both-end hydroxyl group acrylic acid compound polymer which can be produced while controlling a polymer which is only a primary hydroxyl group or a primary and secondary hydroxyl group. It is another object of the present invention to provide a novel both-end hydroxyl group acrylic acid compound polymer in which both end hydroxyl groups are only primary or primary and secondary.

The problems of the present invention are solved by the following invention.
1. A method for producing an acrylic acid compound polymer having hydroxyl groups at both ends, wherein an acrylic acid compound is subjected to a radical polymerization reaction using an OH radical as an initiator.
2. The method for producing an acrylic acid compound polymer having hydroxyl groups at both ends according to the first invention, wherein hydrogen peroxide and a ferrous salt are used as an OH radical generator.

3. The method for producing an acrylic acid compound polymer having a hydroxyl group at both ends of the first or second invention, wherein a mixed solvent of acetonitrile and water is used as a reaction solvent.
4). An acrylic acid compound having a hydroxyl group at both ends of the third invention, wherein the acrylic acid compound is represented by the following formula (1), and an acrylic acid compound polymer having a hydroxyl group at both ends is represented by the following formula (2): Manufacturing method of coalescence. However, in formula, R represents the hydrocarbon group or hydrogen atom which may have a substituent, and x, y represents an integer greater than or equal to 1.

5). The method for producing an acrylic acid compound polymer having a hydroxyl group at both ends of the first or second invention, wherein a mixed solvent of ethanol and water is used as a reaction solvent.
6). An acrylic acid compound having a hydroxyl group at both ends of the fifth invention, wherein the acrylic acid compound is represented by the formula (1), and an acrylic acid compound polymer having a hydroxyl group at both ends is represented by the following formula (3): Manufacturing method of coalescence. However, in the formula, R is the same as described above, and z represents an integer of 2 or more.

7). The manufacturing method of the acrylic acid compound polymer which has a hydroxyl group in the both ends of either of the said 1st-6th invention using a static mixer for a reaction apparatus.

8). An acrylic acid compound polymer having hydroxyl groups at both ends represented by the formula (2). However, in the formula, R, x, and y are the same as described above.
9. An acrylic acid compound polymer having hydroxyl groups at both ends represented by the formula (3). However, in the formula, R and z are the same as described above.

  According to the present invention, the problems of the conventional method for producing an acrylic acid compound polymer having hydroxyl groups at both ends of a molecule (both ends hydroxyl group acrylic acid compound polymer) are solved, and a both-end hydroxyl group acrylic acid compound polymer is produced. be able to.

  That is, according to the present invention, without using a special reaction reagent (chain transfer agent, linking agent, organometallic catalyst, etc.), without introducing atoms (sulfur atom, nitrogen atom, etc.) that lower the physical properties of the polymer, In addition, the hydroxyl group acrylic acid compound polymer at both ends can be produced economically by a simple process by a reaction involving only the raw material compound without requiring special environmental measures. Furthermore, by adjusting the hydroxyl groups at both ends, it becomes possible to easily produce a hydroxyl polymer compound having both terminal hydroxyl groups in which the terminal hydroxyl groups are only primary hydroxyl groups or primary and secondary hydroxyl groups. It is also possible to provide a novel both-end hydroxyl group acrylic acid compound polymer that is only the first grade or the first and second grades.

Hereinafter, the present invention will be described in detail.
The acrylic acid compound used in the present invention is represented by the formula (1). In the formula, R represents a hydrocarbon group or a hydrogen atom which may have a substituent. Examples of acrylic acid compounds include acrylic acid esters and acrylic acid. Among them, acrylic acid esters in which R is the former hydrocarbon group are preferred, and the substituents that the hydrocarbon group may have are It is not involved in the reaction.

  As said hydrocarbon group, a C1-C12 (preferably 1-6) linear or branched alkyl group, a C3-C10 (preferably 5-8) cycloalkyl group, C7-C14 ( Preferably, an aralkyl group having 7 to 12) and an aryl group having 6 to 14 carbon atoms (preferably 6 to 10 carbon atoms) are included, and these include a substituent that does not participate in the reaction (an alkyl group, an aryl group, a halogen atom, an alkoxy group). , A hydroxyl group, an amino group, an epoxy group, etc.), and a hetero atom (oxygen atom, etc.) that does not participate in the reaction may be included in the carbon chain.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group, and each isomer is included. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the aryl group include a phenyl group, And a tolyl group.

Other examples of the hydrocarbon group having a substituent that does not participate in the reaction include 2-ethylhexyl group, 2-methoxyethyl group, 3-methoxybutyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2-aminoethyl. Groups, glycidyl groups,
Perfluoromethyl group, trifluoromethylmethyl group, diperfluoromethylmethyl group, 2-perfluoromethyl-2-perfluoroethylmethyl group,
2-perfluoroethyl group, 2-trifluoromethylethyl group, 2-perfluoroethylethyl group, 2-perfluoroethyl-2-perfluorobutylethyl group, 2-perfluorohexylethyl group, 2-perfluorodecyl Examples include an ethyl group and a 2-perfluorohexadecylethyl group.

  Specific examples of the acrylate ester include those having each of the above-mentioned hydrocarbon groups as R, and also γ- (acryloyloxypropyl) trimethoxysilane and ethylene oxide adducts of acrylic acid. . Among these acrylate esters, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable.

  The OH radical used as an initiator in the present invention can be generated using an OH radical generator. The OH radical generator is not particularly limited as long as it is a compound (or compound system) having the ability to generate OH radicals. Among them, a compound system that decomposes hydrogen peroxide to generate OH radicals is preferable. Examples of such a compound system include a combination of general-purpose compounds in a Fenton reaction using a ferrous salt, an electrolysis reaction on an electrode, a decomposition reaction on a titania catalyst, and the like. From the viewpoints of safety and economy, a system of hydrogen peroxide and ferrous salt, particularly a system of hydrogen peroxide and ferrous sulfate is preferred.

  The amount of the radical generator is not particularly limited as long as the reaction can proceed by generating OH radicals. For example, the amount is 0.5 to 500 mol%, more preferably 5 to 200 mol with respect to the acrylic acid compound. It is preferably in the range of mol%. Further, the use ratio of hydrogen peroxide and ferrous salt may be a normal ratio that generates OH radicals, for example, ferrous salt / hydrogen peroxide is 0.5 to 3.0 on a molar basis, Preferably, it may be about 1.0 to 2.0.

  In the present invention, the acrylic acid compound polymer having hydroxyl groups at both ends (both end hydroxyl acrylic compound polymer) is obtained by using the acrylic acid compound as an initiator (using the OH radical generator as an OH radical). To produce a radical polymerization reaction. At this time, the reaction temperature is preferably −10 to 80 ° C., more preferably 0 to 40 ° C. Moreover, it is preferable to use a reaction solvent, and the amount may be about 1 to 200 times the volume of the acrylic acid compound.

  The reaction solvent is preferably one that is inert to the reaction and dissolves the acrylic acid compound and the OH radical generator to form a homogeneous system. When the OH radical generator is a system of hydrogen peroxide and ferrous salt, the reaction solvent is preferably a mixed solvent of water and an organic solvent, and the ratio is not particularly limited as long as the reaction is not hindered. Examples of the organic solvent include methanol, ethanol, isopropanol, t-butanol, acetonitrile, tetrahydrofuran, 1,4-dioxane, acetone and the like. In this, the mixed solvent of acetonitrile-water and the mixed solvent of ethanol-water are mentioned preferably.

  In the radical polymerization reaction, if the OH radical generator is a system of hydrogen peroxide and ferrous salt, for example, an aqueous solution of one component (ferrous salt) of the radical generator and a radical generator Contact mixture of other components (hydrogen peroxide) and an acrylic acid compound and the reaction solvent, or an aqueous solution of ferrous salt, a mixed solution of hydrogen peroxide and the reaction solvent, and acrylic acid It can be carried out by contact-mixing a compound and a mixed solution of the reaction solvent. After completion of the reaction, the polymer is separated from the reaction mixture by appropriately performing operations such as decantation, extraction, and centrifugation.

  As a reaction apparatus, a radical polymerization reaction (contact mixing of the above two liquids) is performed in a short time so that the production of a polymer (particularly a branched polymer) other than the both-end hydroxyl group acrylic acid compound polymer can be suppressed to 10 wt. What can be performed is preferable, for example, a static mixer is mentioned suitably. As the static mixer, a commercially available one can be used as long as it can supply both the liquids and efficiently contact and mix at the element insertion portion. The reaction time (residence time), the supply speed of both liquids, the inner diameter and length of the element insertion part, the type (or shape) and number of elements, etc., suppress the formation of branched polymers and the like as described above. It adjusts suitably so that it may produce | generate efficiently. For example, if the reaction temperature is room temperature, the residence time may be about 0.1 seconds to 10 seconds.

The both-end hydroxyl group acrylic acid compound polymer is produced as described above. The hydroxyl groups at both ends of this polymer are either primary hydroxyl groups, or one is a primary hydroxyl group and the other is a secondary hydroxyl group. It is. The number average molecular weight (by GPC; polystyrene conversion) is preferably 200 to 10,000, more preferably 300 to 10,000, and particularly preferably 500 to 5,000. When the number average molecular weight is less than 200, the original characteristics of the acrylic acid compound polymer are hardly expressed, and when it exceeds 10,000, handling becomes difficult. The ratio (M _w / M _n ; molecular weight distribution) of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ) is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

  The hydroxyl groups at both ends are adjusted as described above by selecting the reaction solvent, and the corresponding polymers can be obtained. For example, a polymer in which both terminal hydroxyl groups are primary is represented by the above formula (2), and preferably can be obtained by using a mixed solvent of acetonitrile and water as a reaction solvent. And a polymer that is secondary (one is primary and the other is secondary) is represented by the formula (3), and is preferably obtained by using a mixed solvent of ethanol and water as a reaction solvent.

  In the both-end hydroxyl group acrylic acid compound polymer represented by the formula (2), x and y are each a positive integer of 1 or more representing the number of repeating structural units in parentheses, and satisfy the range of x + y. As long as the size is not limited. Here, x + y is an integer of 2 or more (preferably 2 or more and 100 or less) and is related to the number average molecular weight. Moreover, in the both-end hydroxyl group acrylic acid compound polymer represented by the formula (3), z is a positive integer of 1 or more (preferably 1 or more and 100 or less) representing the number of repeating structural units in parentheses. It is related to the number average molecular weight.

  Next, the present invention will be specifically described with reference to examples. The polymer yield was determined with respect to the charged monomer (weight basis), and other evaluations were performed as follows.

1) Molecular structure: Identified by ¹ H-NMR and ¹³ C-NMR spectra. ¹ H-NMR and ¹³ C-NMR were measured under the following conditions.
・ Device: JNMAL400 (JEOL)
・ Solvent: Dimethyl sulfoxide-d (with tetramethylsilane)
・ Temperature: Room temperature

2) Terminal hydroxyl group: Am. Chem. Soc. , 88, 1323 (1966), the series of terminal hydroxyl groups was determined from the ¹⁹ F-NMR spectrum assigned. ¹⁹ F-NMR was measured under the following conditions.
・ Device: JNMAL400 (JEOL)
Solvent: acetone-d
-Reference material: trifluoroacetic acid-Temperature: room temperature

3) Average molecular weight: measured by standard polystyrene conversion method by GPC. Moreover, it changed also by the column and changed also with the standard poly-n-butylacrylate conversion method.
・ Device: LC-10AVP (Shimadzu)
Column: KF-805L (Shodex) x 2 (standard polystyrene conversion method), KF-803L (Shodex) x 2 (standard poly-n-butyl acrylate conversion method)
Solvent: tetrahydrofuran (flow rate 1.0 ml / min)
Sample concentration: 0.2% by weight
・ Temperature: 40 ℃
・ Detector: Differential refractometer

4) Molecular weight: Measured by TOF-MS under the following conditions.
・ Device: T-100LC (JEOL)
・ Ion source: APCI

[Example 1] <Ethyl acrylate / ethanol-water system>
1300 g (0.0500 mol) of ferrous sulfate heptahydrate was placed in a 300 mL flask, and 200 mL of water was added thereto to prepare an aqueous solution (solution A). In another 300 mL flask, 31.6 g A liquid mixture (Liquid B) was prepared by sequentially adding 5.40 g (0.0502 mol) of a weight% hydrogen peroxide solution, 125 mL of water, 75 mL of ethanol, and 5.07 g (0.0506 mol) of ethyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, 12 elements) in which A liquid and B liquid were attached to the confluence of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 700 mm) ) Were simultaneously flown from each flask at a flow rate of 40 mL / min and mixed (polymerization reaction) in a mixer.

After the reaction, the solid in the obtained brown suspension was filtered, the filtrate was concentrated, and water was added to the concentrate to wash the oil. Ethanol is added to dissolve the oily substance after washing, and the oily substance is isolated by repeating concentration and washing twice, and the oily substance after isolation is dried under reduced pressure at 60 ° C. for 15 hours to give a pale yellow viscous liquid (polymer). ) 2.95 g was obtained. The polymer yield was 58%, the number average molecular weight was 727 (molecular weight distribution 2.6) in terms of polystyrene, and 604 (molecular weight distribution 3.0) in terms of poly-n-butyl acrylate. Moreover, when various measurements were performed as described later (Example 4) (measurement results are shown in FIGS. 1 to 5), this polymer has one terminal hydroxyl group and the other terminal hydroxyl group is secondary. It had a structure represented by the above formula (3) which is a hydroxyl group (provided that R = C ₂ H ₅ , z = 5).

[Example 2] <Ethyl acrylate / acetonitrile-water system>
Into a 100 mL flask, 5.58 g (0.0201 mol) of ferrous sulfate heptahydrate was added, and 80 mL of water was added thereto to prepare an aqueous solution (solution A). In another 100 mL flask, 30.8 A liquid mixture (Liquid B) was prepared by sequentially adding 2.20 g (0.0204 mol) of a weight% hydrogen peroxide solution, 80 mL of acetonitrile, and 2.08 g (0.0208 mol) of ethyl acrylate. Next, the liquid A and the liquid B were simultaneously flown in the same manner as in Example 1 and mixed (polymerization reaction) in a mixer.

After the reaction, the same operation as in Example 1 was performed to obtain 0.941 g of a pale yellow viscous liquid (polymer). The yield of the polymer was 45%, the number average molecular weight was 529 (molecular weight distribution 2.1) in terms of polystyrene, and 655 (molecular weight distribution 1.7) in terms of poly-n-butyl acrylate. Further, when various measurements were performed as described later, this polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C _{2 H 5, x + y = 5} ).

[Example 3] <N-butyl acrylate / ethanol-water system>
In a 500 mL flask, 55.6 g (0.2001 mol) of ferrous sulfate heptahydrate was added, and 370 mL of water was added thereto to prepare an aqueous solution (solution A). In another 500 mL flask, 31.6 g A mixed solution (liquid B) was prepared by sequentially adding 22.0 g (0.204 mol) of a weight% hydrogen peroxide solution, 349 mL of ethanol, and 25.6 g (0.200 mol) of n-butyl acrylate. Next, the liquid A and the liquid B were simultaneously flown in the same manner as in Example 1 and mixed (polymerization reaction) in a mixer.

After the reaction, the same operation as in Example 1 was carried out to obtain 8.52 g of a pale yellow viscous liquid (polymer). The polymer yield was 33% and the number average molecular weight was 720 (molecular weight distribution 2.3) in terms of polystyrene. When various measurements were performed as described later, this polymer had a structure represented by the above formula (3) in which one terminal hydroxyl group was a primary hydroxyl group and the other terminal hydroxyl group was a secondary hydroxyl group. (However, R = C ₄ H ₉ , z = 6).

Example 4 <N-butyl acrylate / acetonitrile-water system>
348 g (1.25 mol) of ferrous sulfate heptahydrate was placed in a 5 L glass bottle, and 4.8 L of water was added thereto to prepare an aqueous solution (solution A). In another 5 L glass bottle, 34.2 A liquid mixture (liquid B) was prepared by sequentially adding 62.2 g (0.625 mol) of a weight% hydrogen peroxide solution, 4.6 L of acetonitrile, and 321 g (2.50 mol) of n-butyl acrylate. Next, the liquid A and the liquid B were simultaneously flown in the same manner as in Example 1 and mixed (polymerization reaction) in a mixer.

After the reaction, the same operation as in Example 1 was performed to obtain 37.1 g of a pale yellow viscous liquid (polymer). The polymer yield was 12%, the number average molecular weight was 740 (molecular weight distribution 1.7) in terms of polystyrene, and 727 (molecular weight distribution 1.7) in terms of poly-n-butyl acrylate. ^Also shown ^{1 H-NMR, 13 C-} NMR, 13 C-NMR (DEPT135 °), 19 F-NMR, GPC, the measurement results of the TOF-MS in FIG. 6-11. In addition, ¹⁹ F-NMR was measured by converting the obtained polymer into a terminal trifluoroacetic acid ester as follows. As a result, this polymer had a structure represented by the above formula (2) in which the hydroxyl groups at both ends are primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 6).

<Terminal trifluoroacetate esterification>
In a 50 mL flask equipped with a dropping funnel, 0.500 g of the polymer (0.00172 mol based on the dimer) and 20 mL of dichloromethane were stirred and mixed. Next, 2.40 g (0.0114 mol) of trifluoroacetic anhydride was slowly dropped from the dropping funnel at room temperature, and the mixture was stirred at the same temperature for 15 hours. After completion of the reaction, the solvent was distilled off and dried under reduced pressure at 60 ° C. for 15 hours to obtain 0.556 g of a pale yellow viscous liquid. This pale yellow viscous liquid was subjected to ¹⁹ F-NMR measurement.

[Example 5] <N-butyl acrylate / acetonitrile-water system>
16.7 g (0.0601 mol) of ferrous sulfate heptahydrate was placed in a 500 mL flask, and 295 mL of water was added thereto to prepare an aqueous solution (solution A). In another 500 mL flask, 34.2 A mixed solution (solution B) was prepared by sequentially adding 5.00 g (0.0503 mol) of a weight% hydrogen peroxide solution, 144 mL of water, and 150 mL of acetonitrile. Further, n-butyl acrylate was added to another 500 mL flask. 6 g (0.200 mol) and 271 ml of acetonitrile were added to prepare a mixed solution (solution C). Next, a static mixer (diameter: 4 mm, length: 50 mm, length: 4 mm, length: 50 mm, with three tubes of A liquid, B liquid, and C liquid at room temperature by a tubing pump (equipped with 3 tubes with an inner diameter of 4 mm and a length of 700 mm). 12 elements) were simultaneously flowed from each flask at a flow rate of 40 mL / min and mixed (polymerization reaction) in a mixer.

After the reaction, the same operation as in Example 1 was performed to obtain 2.78 g of a pale yellow viscous liquid (polymer). The yield of the polymer was 11%, and the number average molecular weight was 611 (molecular weight distribution 1.7) in terms of polystyrene. Further, when various measurements were performed as described above, this polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C _{4 H 9, x + y = 5} ).

[Example 6] <n-butyl acrylate / acetonitrile-water system>
A 5 L flask was charged with 55.6 g (0.200 mol) of ferrous sulfate heptahydrate, and 2 L of water was added thereto to prepare an aqueous solution (solution A). In another 5 L flask, 30.9 g A liquid mixture (Liquid B) was prepared by sequentially adding 22.1 g (0.201 mol) by weight of hydrogen peroxide, 1.95 L of acetonitrile, and 25.6 g (0.200 mol) of n-butyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, element, in which liquid A and liquid B were attached to the junction of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 1.4 m). 12) were simultaneously flown from each flask at a flow rate of 100 mL / min and mixed in a mixer (polymerization reaction), and the reaction solution was dropped into a 10 L beaker filled with 4 L of n-hexane. After the reaction, 400 g of sodium chloride was introduced into the obtained brown suspension, and the acetonitrile phase was separated. After separation, n-hexane washing was repeated until no monomer was present, followed by extraction with diethyl ether and drying with magnesium sulfate. The solvent was distilled off to obtain 10.4 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 50%, and the yield of the polymer was 41%. In addition, 22 g of liquid mixture is extract | collected from the exit part of a mixer, and the conversion rate is the monomer density | concentration (0.05 mol / l = 0.71 wt%) with the monomer density | concentration (calculated from GC internal standard calibration curve method) after reaction. It was calculated from the ratio. The number average molecular weight of the obtained polymer was 527 (molecular weight distribution 2.3) in terms of polystyrene, and after changing the GPC column to Shodex: KF-402.5HQ × 2, it was 678 (molecular weight in terms of poly-n-butyl acrylate). Distribution 1.4). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 5).

[Example 7] <N-butyl acrylate / acetonitrile-water system>
Except for the flow rate of 200 mL / min, mixing and post-treatment operations were performed in the same manner as in Example 6 to obtain 10.1 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 52%, and the yield of the polymer was 39%. The number average molecular weight of the obtained polymer was 505 (molecular weight distribution 1.8) in terms of polystyrene, and after changing the GPC column to Shodex: KF-402.5HQ × 2, it was 645 (molecular weight in terms of poly-n-butyl acrylate). Distribution 1.3). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 5).

[Example 8] <N-butyl acrylate / acetonitrile-water system>
11.1 g (0.0400 mol) of ferrous sulfate heptahydrate was placed in a 5 L flask, and 2 L of water was added thereto to prepare an aqueous solution (solution A). A liquid mixture (Liquid B) was prepared by sequentially adding 4.41 g (0.0401 mol) of a weight% hydrogen peroxide solution, 1.99 L of acetonitrile, and 5.13 g (0.0400 mol) of n-butyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, element, in which liquid A and liquid B were attached to the junction of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 1.4 m). 12) were simultaneously flown from each flask at a flow rate of 200 mL / min and mixed in a mixer (polymerization reaction), and the reaction solution was dropped into a 10 L beaker filled with 4 L of n-hexane. After the reaction, 400 g of sodium chloride was introduced into the obtained brown suspension, and the acetonitrile phase was separated. After separation, n-hexane washing was repeated until no monomer was present, followed by extraction with diethyl ether and drying with magnesium sulfate, and the solvent was distilled off to obtain 0.72 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 30%, and the yield of the polymer was 14%. In addition, 25 g of liquid mixture was extract | collected from the exit part of a mixer, and the conversion rate was prepared monomer concentration (0.01 mol / l = 0.14 wt%) and monomer concentration after reaction (calculated from GC internal standard calibration curve method). It was calculated from the ratio. The number average molecular weight of the obtained polymer was 277 (molecular weight distribution 1.8) in terms of polystyrene, and after changing the GPC column to Shodex: KF-402.5HQ × 2, 412 (molecular weight in terms of poly-n-butyl acrylate) Distribution 1.3). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups are primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 3).

[Example 9] <N-butyl acrylate / acetonitrile-water system>
A 5 L flask was charged with 55.6 g (0.200 mol) of ferrous sulfate heptahydrate, and 2 L of water was added thereto to prepare an aqueous solution (solution A). In another 5 L flask, 30.9 g A liquid mixture (liquid B) was prepared by sequentially adding 22.1 g (0.201 mol) by weight of hydrogen peroxide, 0.95 L of acetonitrile, 1 L of water, and 25.6 g (0.200 mol) of n-butyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, element, in which liquid A and liquid B were attached to the junction of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 1.4 m). 12) were simultaneously flown from each flask at a flow rate of 200 mL / min and mixed in a mixer (polymerization reaction), and the reaction solution was dropped into a 10 L beaker filled with 4 L of n-hexane. After the reaction, 600 g of sodium chloride and 1 L of acetonitrile were introduced into the resulting brown suspension, and the acetonitrile phase was separated. After liquid separation, washing with n-hexane was repeated until the monomer disappeared, followed by extraction with diethyl ether and drying with magnesium sulfate, and the solvent was distilled off to obtain 15.2 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 66%, and the yield of the polymer was 59%. In addition, 24 g of liquid mixture was extract | collected from the exit part of a mixer, and the conversion rate was prepared monomer concentration (0.05 mol / l = 0.67 wt%) and the monomer concentration after reaction (calculated from GC internal standard calibration curve method). It was calculated from the ratio. The number average molecular weight of the obtained polymer was 689 (molecular weight distribution 9.0) in terms of polystyrene, and after changing the GPC column to Shodex: KF-402.5HQ × 2, it was 801 (molecular weight in terms of poly-n-butyl acrylate). Distribution 2.1). This polymer had a structure represented by the formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 6).

[Example 10] <N-butyl acrylate / acetonitrile-water system>
A pale yellow viscous liquid (polymer) 14 was prepared in the same manner as in Example 9 except that 600 mL of a saturated aqueous sodium hydrogen carbonate solution was added to a 10 L beaker filled with 3.4 L of n-hexane and the reaction solution was dropped here. .5 g was obtained. The conversion rate at this time was 69%, and the yield of the polymer was 57%. The number average molecular weight of the obtained polymer was 744 (molecular weight distribution 18.7) in terms of polystyrene, 934 (molecular weight in terms of poly-n-butyl acrylate) after changing the GPC column to Shodex: KF-402.5HQ × 2. Distribution 3.5). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 7).

[Example 11] <N-butyl acrylate / acetonitrile-water system>
33.4 g (0.120 mol) of ferrous sulfate heptahydrate was placed in a 5 L flask, and 2 L of water was added thereto to prepare an aqueous solution (liquid A). In another 5 L flask, 30.9 g A mixed liquid (liquid B) was prepared by sequentially adding 13.3 g (0.121 mol) of a weight% hydrogen peroxide solution, 1.97 L of acetonitrile, and 15.4 g (0.120 mol) of n-butyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, element, in which liquid A and liquid B were attached to the junction of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 1.4 m). 12) were simultaneously flown from each flask at a flow rate of 200 mL / min and mixed in a mixer (polymerization reaction), and the reaction solution was dropped into a 10 L beaker filled with 3.4 L of n-hexane and 400 mL of saturated sodium bicarbonate. . After the reaction, 400 g of sodium chloride was introduced into the obtained brown suspension, and the acetonitrile phase was separated. After separation, n-hexane washing was repeated until no monomer was present, followed by extraction with diethyl ether and drying with magnesium sulfate. The solvent was distilled off to obtain 10.4 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 50%, and the yield of the polymer was 41%. In addition, 24 g of liquid mixture is extract | collected from the exit part of a mixer, and the conversion rate is the monomer concentration (0.03 mol / l = 0.43 wt%) and monomer concentration after reaction (calculated from GC internal standard calibration curve method). It was calculated from the ratio. The number average molecular weight of the obtained polymer was 395 (molecular weight distribution 3.1) in terms of polystyrene, the GPC column was changed to Shodex: KF-402.5HQ × 2, and then 636 (molecular weight in terms of poly-n-butyl acrylate). Distribution 1.7). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 5).

[Example 12] <N-butyl acrylate / acetonitrile-water system>
A 5 L flask was charged with 89.0 g (0.320 mol) of ferrous sulfate heptahydrate, and 2 L of water was added thereto to prepare an aqueous solution (solution A). In another 5 L flask, 30.9 g A mixed liquid (liquid B) was prepared by sequentially adding 35.3 g (0.321 mol) of a weight% hydrogen peroxide solution, 1.92 L of acetonitrile, and 41.1 g (0.321 mol) of n-butyl acrylate. Next, a static mixer (4 mm in diameter, 50 mm in length, element, in which liquid A and liquid B were attached to the junction of both liquids at room temperature by a tubing pump (equipped with 2 tubes with an inner diameter of 4 mm and a length of 1.4 m). 12) were simultaneously flown from each flask at a flow rate of 200 mL / min and mixed in a mixer (polymerization reaction), and the reaction solution was dropped into a 10 L beaker filled with 3.4 L of n-hexane and 600 mL of saturated sodium bicarbonate. . After the reaction, 400 g of sodium chloride was introduced into the obtained brown suspension, and the acetonitrile phase was separated. After the separation, n-hexane washing was repeated until the monomer disappeared, followed by extraction with diethyl ether and drying with magnesium sulfate, and the solvent was distilled off to obtain 14.9 g of a pale yellow viscous liquid (polymer). The conversion rate at this time was 46%, and the yield of the polymer was 36%. In addition, 24 g of liquid mixture is extract | collected from the exit part of a mixer, and the conversion rate is the monomer concentration (0.08 mol / l = 1.13 wt%) and monomer concentration after reaction (calculated from GC internal standard calibration curve method). It was calculated from the ratio. The number average molecular weight of the obtained polymer was 471 (molecular weight distribution 2.2) in terms of polystyrene, the GPC column was changed to Shodex: KF-402.5HQ × 2, and then 711 (molecular weight in terms of poly-n-butyl acrylate). Distribution 1.4). This polymer had a structure represented by the above formula (2) in which both terminal hydroxyl groups were primary hydroxyl groups (provided that R = C ₄ H ₉ , x + y = 5).

  An acrylic acid compound polymer having a hydroxyl group at both ends can easily convert the hydroxyl group to another functional group, and further makes the polymer linear or network-like by utilizing the reactivity of the hydroxyl group. Therefore, a high molecular compound having good physical properties such as toughness, heat resistance, weather resistance, and durability can be obtained. Therefore, when such a polymer having hydroxyl groups at both ends is used as various resin raw materials, there is no unreacted material that impairs the physical properties of the material, and all polymers are reliably incorporated into the resin cross-linked structure. It is very useful as a raw material for various resins such as polyester resins, polyurethane resins and polycarbonate resins, and as a raw material for reactive diluents such as paints, adhesives, sealing materials and urethane foams.

  In particular, an acrylic acid compound polymer having primary hydroxyl groups at both ends has a higher reactivity of primary hydroxyl groups than secondary and tertiary hydroxyl groups, and it is easy to form a resin cross-linked structure. In addition, the cross-linked site (ester bond, amide bond, etc.) formed through the primary hydroxyl group can be cleaved more than the bond formed through the secondary hydroxyl group or tertiary hydroxyl group. Therefore, there is an advantage that a resin having high durability, weather resistance, heat resistance and the like can be obtained.

The measurement result of ¹ H-NMR of the polymer obtained in Example 1 is shown. The measurement result of ¹³ C-NMR of the polymer obtained in Example 1 is shown. The measurement result of ¹³ C-NMR (DEPT135 °) of the polymer obtained in Example 1 is shown. The measurement result of ¹⁹ F-NMR of the polymer obtained in Example 1 is shown. The measurement result of GPC of the polymer obtained in Example 1 is shown. The measurement result of ¹ H-NMR of the polymer obtained in Example 4 is shown. The measurement result of ¹³ C-NMR of the polymer obtained in Example 4 is shown. The measurement result of ¹³ C-NMR (DEPT135 °) of the polymer obtained in Example 4 is shown. The measurement result of ¹⁹ F-NMR of the polymer obtained in Example 4 is shown. The measurement result of GPC of the polymer obtained in Example 4 is shown. The measurement result of TOF-MS of the polymer obtained in Example 4 is shown.

Claims (9)

A method for producing an acrylic acid compound polymer having hydroxyl groups at both ends, wherein an acrylic acid compound is subjected to a radical polymerization reaction using an OH radical as an initiator. The method for producing an acrylic acid compound polymer having hydroxyl groups at both ends according to claim 1, wherein hydrogen peroxide and ferrous salt are used as an OH radical generator. The method for producing an acrylic acid compound polymer having hydroxyl groups at both ends according to claim 1 or 2, wherein a mixed solvent of acetonitrile and water is used as a reaction solvent. An acrylic acid compound having hydroxyl groups at both ends according to claim 3, wherein the acrylic acid compound is represented by the following formula (1), and an acrylic acid compound polymer having hydroxyl groups at both ends is represented by the following formula (2). Manufacturing method of coalescence. (In the formula, R represents a hydrocarbon group or a hydrogen atom which may have a substituent, and x and y represent an integer of 1 or more.)

The method for producing an acrylic acid compound polymer having hydroxyl groups at both ends according to claim 1 or 2, wherein a mixed solvent of ethanol and water is used as a reaction solvent.

The acrylic compound compound having a hydroxyl group at both ends according to claim 5, wherein the acrylic compound is represented by the formula (1), and an acrylic acid compound polymer having hydroxyl groups at both ends is represented by the following formula (3). Manufacturing method of coalescence. (In the formula, R is the same as described above, and z represents an integer of 2 or more.) The manufacturing method of the acrylic acid compound polymer which has a hydroxyl group in both the ends in any one of Claims 1-6 which uses a static mixer for a reaction apparatus. An acrylic acid compound polymer having hydroxyl groups at both ends represented by the formula (2). (In the formula, R, x and y are the same as described above.) An acrylic acid compound polymer having hydroxyl groups at both ends represented by the formula (3). (In the formula, R and z are the same as described above.)

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